30 January 2015
1K UV-A Automotive Refinish;
Clear Coats and Primers
Michael J. Dvorchak
Phone: 404-719-8912
E-Mail: Michael.Dvorchak@allnex.com
www.allnex.com
1
Introducing Allnex!
2
Outline
• Changes in the automotive OEM and refinish markets
• Introduction of UV-A curable auto refinish
• Current products and innovation in the market
• Future outlook for the UV–A curable refinish market
• Conclusions
• References
• Questions
3
Changes in the Automotive OEM and Refinish Markets
• Major changes in polymers technologies used in coatings
• NC lacquers were acceptable when the only color option was black
• 2 K reactive primers, clear coats, water based “base coats”
• Lower VOC and VHAPS
• Major changes in substrate technologies
•
•
•
•
Cold rolled steel
Engineered plastics
Aluminum
Composites
NC lacquers
Base Coat; smokey quartz
4
Introduction of UV–A Auto Refinish
• Early attempts to develop a UV refinish clear coat (2K) 1
• UV Flash lamp (Xe lamp @ 480 nm) used in conjunction with BAPO PI
• Polymer chemistry was dual cure (R-N=C=O; R-C=C & R-OH)
• Cure took place with 10 to 20 flashes
• Patent application on a UV-A primer in 2001 (1K) 2
• UV A lamp source was 250 W iron doped source filtering out UV B, UV C
• Polymer chemistry was mono-cure (R-C=C)
• Cure took place in several minutes leaving an uncured surface due to oxygen
inhibition
• Solvent wipe required
Photo provided by I-CAR
5
Introduction of UV–A Auto Refinish
• Automotive OEM technical paper on UV auto refinish clear coats 3
• OEM evaluates UV cure clear coats
• HALS and UVAs were formulated into these clear coats
• OEM found that these systems embrittled to unacceptable levels under
accelerated weathering
• 2003 Patent application by a paint company on UV–A (1K) CC 4
•
•
•
•
UVA/UVV & UV–A only curable
Polymer chemistry was mono-cure (R-C=C)
Cure times were 4 minutes with no surface inhibition
No gloss reduction or cracking was found when subjected to SAEJ1960
6
Introduction of UV–A Auto Refinish
• 2003 RADTECH report on use of UV–A cure primer systems in body
shops 5
• The following benefits were noted in the report: 1) time savings of 25 to 88 % on
each job, 2) less preparation time, 3) use of disposable utensils is reduced, 4) less
masking, 5) no flash times required between layers and 6) less waste over a 2K
system
• Report states the need for a UV–A clear coat
• 2005 OEM/Refinish paint company awarded the US Presidential Green
Chemistry award for UV-cured auto finishing paint
Photo provided by I-CAR
7
Introduction of UV–A Auto Refinish
• 2006 patent application on dual cure UV clear coat spot repair 6
• UV–A light source used for cure
• Polymer chemistry was dual cure (R-N=C=O; R-C=C & R-OH)
• After cure, the surface was easily polishable without defects
• 2006 patent filed by an auto OEM paint company on a UV–A primer
that has a high pigmentation levels and extremely low oxygen
inhibition 7
•
•
•
•
Uses a 400 W UV–A light that is held 10 to 30 cm away from the substrate
Chemistry is a mono-cure technology (R-C=C)
Cure time is 1-3 minutes at a thickness of 200 microns
Patent reports the ability to sand the primer after UV curing and the coating
has had time to cool
8
Introduction of UV–A Auto Refinish
• Auto OEM technical paper on scratch performance of three UV
cure automotive refinish clear coats 8
• Three UV cure clear coats tested against a thermally cured acrylic/melamine/silane
clear coat.
• Car wash performance testing by the AMTEC-Kistler showed that two of the UV cure
clear coats performed better than the acrylic/melamine/ silane clear coat.
9
Introduction of UV – A Auto Refinish
• Patent filed in 2007 that uses a structure to cure the UV paint 9
• Patent publication filed in 2009 on a UV cure spot blender for clear
coats 10
• Uses a UV–A 400 lamp to cure the UV clear coat
• Chemistry is based on 2K dual cure or 3K dual cure thiolene-based technology
• Clear coat technology is cured for 5 minutes at a distance of 10 inches
Photo provided by I-CAR
10
Introduction of UV – A Auto Refinish
• OEM awarded the 2010 RADTECH Emerging Technology Award for the
use of an in-line UV spot repair 11
• The UV cure technology could possible reduce their cycle time by 50%
• OEM evaluating the process to see if this technology will meet the durability
specifications and test protocols.
• Facilities would have to be modified to use the UV cure technology
Photo provided by I-CAR
11
Current Products and Innovation in the Market
High throughput formulation screening 12,13
1:1
Resin/ 50:50 blend
Symplex lattice design
Delta
Fox Trot
Echo
Hotel
Charlie
Delta/Fox Trot
Delta/Echo
Delta/Charlie
Fox Trot/Echo
Fox Trot/Echo
Fox Trot /Hotel
Fox Trot / Charlie
Echo / Hotel
Echo / Charlie
Hotel / Charlie
Reactive
diluent
[PI]
Photoinitiator/blend
HDDA Irgacure 184 #
4%
TPGDA Irgacure 500 #
1%
TMPTA Irgacure 500 #/Amine synergist
Darocur 1173 #
CGI 1870 #
Irgacure 819 #
Irgacure 1850 #
Darocur 4265 #
Irgacure 184/Darocur 1173
Genacure ITX +
Irgacure500/Amine synergist/Irgacure 819
Genacure ITX/ CGI 1870
Irgacure 1300 #
Irgacure 1700 #
Irgacure 2959 #
D-optimal design including 2nd order interactions:
~ 500 formulations and ~ 24,000 films (5 weeks of experimentation)
# BASF, + Rahn
Irradiation
time [sec]
0
8
20 4
60
180
Distance
from lamp
Current Products and Innovation in the UV-A Refinish Market
Echo/Hotel
Echo/Charlie
Echo
Hotel/Charlie
Hotel
Fox Trot/Echo
Fox Trot/Hotel
Fox Trot/Charlie
Fox Trot
Delta/Echo
Delta/Hotel
Delta/Fox Trot
Delta/Charlie
Delta
Charlie
1870
1173
1870/ITX
ITX
4265
1700
1300
184/1173
184
2959
1850
500/Amine
500
819
500/819/Amine
The larger the bubble shows the least amount of surface inhibition after UV cure
Current Products and Innovation in the Market
Photo micrograph of a blend line for a commercially available
UV – A curable clear coat over a black base coat
14
Current Products and Innovation in the Market
Concept of matching the Tg’s of traditional 2 K clear coat technology with a
1K UV A cure clear coat 14
Resin
°C
UA Resin A
UA Resin B
UA Blend 1
UA Blend 2
UA Blend 3
UA Blend 4
UA Blend 5
Commercial UV Refinish
Commercial 2K Refinish
10
104
103
105
106
84
74
101
62
isocyanurate
allophanate
O
O
R
O
N
N
N
R
R
O
O
N
O
N
H
1
2
O
R= -(CH2)6 N
H
O
intramolecular
H-bridge
R
R
O
O
O
O
15
Current Products and Innovation in the Market
Blend line
Blend line
Photo micrograph of a blend line for a commercially
available 2K Clear Coat over a black base coat
Photo micrograph of a blend line for a
UV – A Cure Clear Coat
After matching Tg of a
2K Clear Coat over a black base coat
16
Current Products and Innovation in the Market
Photograph of a 1K UV-A primer and a 1K UV-A
Clear Coat after 8 years of service in the NE US
Photograph of a 2K traditional primer and Clear Coat
that was used as the standard for testing on the
same vehicle
17
Future Outlook for the UV–A Curable Refinish Market
• Driving Change event in 2003 15
• Over 130 industry personnel attended
• The future looked bright over 10 years ago
• RADTECH Transportation Focus Group & I-CAR
• In 2007 RADTECH ( industry trade organization) teamed up with I-CAR (auto
refinish professional training organization) to develop a web based training module
devoted to UV-A auto refinish
• Since this launch over 900 professional body repair technicians have paid to take
this unique training program
• The future of 1K UV–A cure is tied to the introduction of a 1K UV-A
cure clear coat 16
Photo provided by I-CAR
18
Conclusions
• A significant amount of work has been done trying to develop the
market for 1K UV-A Primers and Clear Coats
• When polymer technology went from NC lacquers to 2K reactive
system, there was a lot of resistance to change
• The difficulty to repair was the major resistance to change from NC
lacquers to a 2K reactive system
• In time better acceptance of the 1K UV-A Primers and Clear Coats
will occur
19
References
1.) K.Magg, et al., Progress in Organic Coatings 40 (2000) 93-97
2.) D. Fenn, et al., US 6,838,177 Mar. 27, 2003
3.) M. Nichols, et al., RADTECH Report Nov/DEC 2001
4.) D. Braun, et al., US 2005/0095371 May 5, 2005
5.) D. Maloney, RADTECH Report NOV/DEC 2003
6.) B. Lettmann, et al., US 7,683,105 Mar. 23, 2010
7.) J. O’Neil, US 8,227,050 Jul. 24, 2012
8.) C. Seubert, et al., J. Coat. Technol. Res., 4 (1) 21-30, 2007
9.) K. DeRegge, et al., US 7,704,564 Apr. 27, 2010
10.) M. Bowman, et al., US 2011/0097481 Apr. 28, 2011
11.) Ford Motor Company, 2010 Emerging Technology Award, RADTECH 2010 Conference
12.) H. Bach, et al., RADTECH Europe, Nov. 2003
13.) S. Strazisar, et al., RADTECH Report, Nov. 2003
14.) M. Jeffries, et al., RADTECH 2/5 2006, Apr. 2006
15.) RADTECH NA sponsored event; Driving Change, Sept. 2003
16.) H.-B. Gia, WO 2009/039137 Mar. 26, 2009
20
Thank you for your attention!
For more information, please visit us at www.allnex.com.
Contact Name:
Cell Phone:
E-mail:
www.allnex.com
Michael J. Dvorchak
404-719-8912
Michael.Dvorchak@allnex.com
www.allnex.com
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Back Up Slides
Light Output Readings After UV A Cure Refinishing of PC
• 1993 Dodge Sundance
• Readings at low audit settings
• High beam 17,000 Candla
• Prior value = 7,000 Candla
• Low beam 7,000 Candla
• Prior value = 3,000 Candla
Many military equipment / vehicles use polycarbonate as replacement for glass
due to its performance for bullet resistance and light weight.
Stencil UV A Coating F-16
C-130; Small Area Repair UV A
Military Applications
UV A Cure Battle Field Composite
Repair
• KISS Principle
• Ballistic holes in composites
- AK-47 or shrapnel
• Quick return to service
• Simple and quick process that returns the
aircraft to service with eventual
permanent repair at the depot
• Commercial air lines interested is this
technique for remote location repair
Basics of UV Curing
Curing of Coatings with electromagnetic radiation
Curing conditions
seconds/ milliseconds
UV- or electron
beam curing
Source: Bürkle
Electron beam
< 1 nm
X- Rays
< 100 nm
UV-C
100 - 280 nm
Imperative for the polymerization
of printing inks and varnishes for a
complete curing.
UV light
< 400 nm
wave length
UV-B
280- 315 nm
Supports and maintains the
triggered off reactions and
ensures a better curing
because of longer waves.
Visible light
> 400 nm
IR
> 800 nm
UV-A
315 - 380 nm
Responsible for the curing of very
thick layers
Low Energy UV-A Lamps
Philips TL03
Promotor Car 250
Honle 250
Panacol 250
UV Process Supply 400
H&S Autoshot 400
Low Intensity Microwave Lamp
• Quantum Technologies
• Low powered lamps
• Current UV-A lamp
assembly has a series of
bulbs from 320 to 400 nm
• Bulbs can be made to
desired wavelength output
NEW UV-A Light Sources
Automotive Refinish/Aerospace & Printing
• 1,200 W UVA Light
• LED UVA
• H & S Auto Shot
• Phoseon Technology